Population of the most relevant ELF valence basins, C1[3]–C5[4] forming bond distances and relative energies^a, of the reagents, stationary points and the selected points of the IRC involved in the formation of the new C1[3]–C5[4] single bonds along the most favorable 6-exo reaction path associated with the non-polar 32CA reactions between 1H-phosphorinium-3-olate 1a with MMA. The electron populations are given in average number of electrons, e, distances in angstroms, Å, and relative energies in kcal mol⁻¹.

Points	1a	MMA	MC6x-H	TS6x-H	P6′	P7	P9′	P10	CA6x-H
Phases				IV	VII	VIII	X	XI
d(C1–C5)			4.086	2.163	1.987	1.975	1.560	1.559	1.556
d(C3–C4)			6.712	3.235	3.182	3.179	2.072	2.060	1.571
ΔE			−5.3	7.0	5.8	5.6	−24.6	−25.0	−47.9
V(C1,P2)	1.80		1.87	2.59	2.14	2.12	1.85	1.85	1.81
V′(C1,P2)	1.89		1.85
V(P2)				1.88	1.98	1.98	2.32	2.31	2.36
V(P2,C3)	1.56		1.63	2.55	2.54	2.53	1.99	1.98	1.82
V′(P2,C3)	1.66		1.61
V(C4,C5)		1.67	1.73	3.22	2.80	2.76	2.00	2.00	1.90
V′(C4,C5)		1.81	1.73
V(C1)					0.51
V(C5)					0.36
V(C3)							0.77
V(C4)							0.58
V(C1,C5)						0.90	1.77	1.77	1.81
V(C3,C4)								1.37	1.83

^aRelative to the separate reagents, 1a and MMA.